Triblock copolymers—continued

Morphology of the anionically synthesized triblock copolymers of polyfp-methyl-styrene) and PDMS and their derivatives obtained by the selective chlorination of the hard segments were investigated by TEM 146). Samples with low PDMS content (12%) showed spherical domains of PDMS in a poly(p-methylstyrene) matrix. Samples with nearly equimolar composition showed a continuous lamellar morphology. In both cases the domain structure was very fine, indicating sharp interfaces. Domain sizes were estimated to be of the order of 50-300 A. 

FIGURE 5.7 Phase separation in styrene-butadiene-styrene (SBS) triblock copolymer. The isolated spherical styrene domains form the hard phase, which act both as intermolecular tie points and filler. The continuous butadiene imparts the elastomeric characteristics to this polymer. MW = molecular weight. (From Grady, B.P. and Cooper, S.L., Science and Technology of Rubber, Mark, J.E., Erman, B., and Eirich, F.R. (eds.). Academic Press, San Diego, CA, 1994. With permission.)... 

The living nature of PCL obtained in the presence of Zn(OAl-(OPri)2)2 has been used to prepare both di- and triblock copolymers of e-caprolactone and lactic acid (42,43). Treatment of the initial living PCL with dilactide afforded a PCL-PLA diblock with M /Mn = 1.12, with each block length determined by the proportions of the reactants, i.e., the ratio of [monomer]/[Zn]. While the living diblock copolymer continued to initiate dilactide polymerization, it failed to initiate e-caprolactone polymerization. To obtain a PCL-PLA-PCL triblock, it was necessary to treat the living PCL-PLA-OAIR2 intermediate with ethylene oxide, then activate the hydroxy-terminated PCL-PLA-(OCH2CH2)nOH with a modified Teyssie catalyst (Fig. 5). 

The use of lightly crosslinked polymers did result in hydrophilic surfaces (contact angle 50°, c-PI, 0.2 M PhTD). However, the surfaces displayed severe cracking after 5 days. Although qualitatively they appeared to remain hydrophilic, reliable contact angle measurements on these surfaces were impossible. Also, the use of a styrene-butadiene-styrene triblock copolymer thermoplastic elastomer did not show improved permanence of the hydrophilicity over other polydienes treated with PhTD. The block copolymer film was cast from toluene, and transmission electron microscopy showed that the continuous phase was the polybutadiene portion of the copolymer. Both polystyrene and polybutadiene domains are present at the surface. This would probably limit the maximum hydrophilicity obtainable since the RTD reagents are not expected to modify the polystyrene domains. 

While the morphology of AB-type block copolymers is limited to a relatively small number of possibilities, the morphology of ABC triblock copolymers is considerably richer and complex (Bates and Fredrickson, 1999). New, exotic, and often unexpected phases are continually being discovered by ex-perimentahsts (Breiner et al., 1998). There is a need for theoretical methodology that is capable of predicting, a priori, the possible new morphologies in these more complex block copolymers. We describe one such method in this article. 

Lynch, I. and PiculeU, L. (2004) Size, concentration, and solvency effects on the viscosifying behavior of PEO-PS-PEO triblock copolymers in AOT oU-continuous microemulsions. J. Phys. Chem. B, 108, 7515-7522. 

Scalco, Huseby, and Blyler (8), Zosel (9), and Bergen and Morris (10). Prest and Porter (23) applied the same principle to homopolymer blends [poly (2,6-dimethylphenylene oxide)-polystyrene]. Recently some papers were published on triblock copolymers of styrene-butadiene-styrene and on their blends with polybutadiene (24, 25). Triblock copolymers can be considered heterophase material as the different constituent blocks are thermodynamically incompatible with each other, and, consequently, polystyrene domains are enclosed in polybutadiene (continuous matrix). The findings indicate that these systems are in general thermorheologically complex, so that the shift factor ar depends not only on temperature but also on time. These conclusions have been extrapolated to other two-phase systems. 

HIPS, PE, and either SBS or SIS a co-continuous morphology SMMA and either a mixture of SBS and a tapered BSB triblock copolymer, or SBR... 

The thermoplastic IPNs utihze physical cross-hnks, rather than chemical crosshnks. Usually, these materials wiU flow when heated to sufficiently high temperature (hence the terminology thermoplastic), but behave as thermosets at ambient temperature, with IPN properties, often possessing dual phase continuity. Most often, physical crosshnks are based on triblock copolymers (thermoplastic elastomers being the leading material), ionomers, or semi-crystalhne materials. 

This ABA-type triblock copolymer was used as a drug release depot for continuous release of hiunan insulin and of glucagons-like peptide-1 (GLP-1). The observation of both reduced initial burst and a constant release of hmnan insulin from ReGel in vitro is due to the domain structure of the gel and to the modification of the association states of insulin by zinc. Animal studies using SD rats were performed to verify the release profile of insuhn from this ABA block copolymer hydrogel. ReGel formrdation maintained insulin release for up to 15 days, which could allow diabetic patients to reduce the number of insulin injections to two per month for basal insulin requirements (31). 

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